Deterministic feedback blender

ABSTRACT

Methods and systems for high precision, continuous blending of mixtures, and particularly mixtures having at least two distinct chemical components, are disclosed. More particularly, the disclosed methods and systems provide high precision, continuous blending of buffered oxide etch mixtures containing water, ammonium fluoride, and hydrofluoric acid.

TECHNICAL FIELD

Methods and systems for high precision, continuous blending of mixtures,and particularly mixtures having at least two distinct chemicalcompounds, are disclosed. More particularly, the disclosed methods andsystems provide high precision, inline blending of, among others,buffered oxide etch mixtures containing water, ammonium fluoride, andhydrofluoric acid.

BACKGROUND

In various industries, chemical delivery systems are used to supplychemicals to processing tools. Illustrative industries include thesemiconductor, pharmaceutical, biomedical, food processing, householdproduct, personal care product, or petroleum industries.

The chemicals being delivered by a given chemical delivery systemdepend, of course, on the particular processes being performed.Accordingly, the particular chemicals supplied to a semiconductorprocessing tool depend upon the processes being performed inside thetool. Illustrative semiconductor processes include etching, cleaning,chemical mechanical polishing (CMP), and wet deposition (e.g., spin-on,copper electroless, electroplating, etc.).

Commonly, two or more fluids are combined to form the desired mixturefor the particular process. The mixtures may be prepared in batches, on-or off-site, and then shipped to the processing location. Alternatively,the mixtures may be prepared at the point-of-use using a suitableblender system.

U.S. Pat. No. 6,050,283 to Air Liquide America Corp. discloses a systemand method for mixing and/or diluting ultrapure fluids, such as liquidacids, for semiconductor processing.

U.S. Pat. No. 6,799,883 to Air Liquide America L.P. discloses a methodand apparatus for continuously blending a chemical solution for use insemiconductor processing.

U.S. Pat. No. 6,923,568 to Celerity, Inc. discloses a method andapparatus for blending and supplying process materials, particularlyultra-high purity chemicals.

U.S. Pat. No. 7,344,297 to Air Liquide Electronics U.S., LP, discloses amethod and apparatus for asynchronous blending and supply of chemicalsolutions.

A need remains for methods and systems for high precision, continuousblending of solutions.

NOTATION AND NOMENCLATURE

Certain abbreviations, symbols, and terms are used throughout thefollowing description and claims, and include:

As used herein, the indefinite article “a” or “an” means one or more.

As used herein, the terms “approximately” or “about” mean±2% of thevalue stated.

As used herein, the term “inline” or “continuous” means that theblending process substantially simultaneously feeds the chemicals towhile removing the product mixture from a mixing zone withoutinterruption. The inline blending process is distinct from a “batch”process, in which defined quantities of chemicals are mixed, typicallyin a mixing tank, to produce a batch, or specific quantity, of theproduct mixture.

As used herein, the term “slurry” means a chemically active or bufferedsolution containing suspended solids. Slurries are typically used toremove and/or planarize deposited materials.

As used herein, the term “species” means atoms, molecules, molecularfragments, ions, etc. resulting from the methods disclosed. In otherwords, the disclosed blending methods of any of the components, fluids,acids, bases, oxidizers, reducers, or chemicals disclosed herein mayproduce species (i.e., atoms, molecules, molecular fragments, ions,etc.) of the item subject to blending.

As used herein, the phrase “maintaining a target concentration in themixture of Component X within # % w/w” means not permitting theconcentration of the mixture to exceed the # % w/w difference from thetarget concentration.

SUMMARY

Inline blending methods are disclosed. The components that are blendedmay alter each other's assays, complicating the standard inline blendingprocesses which typically mix components based on volume or mass.Component A, Component B, and a solvent are mixed in an inline blenderto form a mixture. The mixture is analyzed downstream of the inlineblender to determine the concentration of Component A and theconcentration of Component B. A target concentration in the mixture ofComponent A is maintained within 0.008% w/w and a target concentrationin the mixture of Component B is maintained within 0.22% w/w byadjusting the flow rate of Component A, Component B, and/or the solventbased on the concentration of Component A and the concentration ofComponent B. The disclosed inline blending methods may include one ormore of the following aspects:

-   -   maintaining the target concentration notwithstanding the source        of Component A and/or Component B and/or the solvent;    -   the mixture being a solution;    -   the mixture being a slurry;    -   the slurry comprising a basic solution;    -   the slurry comprising an acidic solution;    -   the slurry comprising abrasive particles;    -   the abrasive particles being silica (SiO₂), alumina (Al₂O₃),        calcium carbonate (CaCO₃), ceria (CeO₂), zirconia (ZrO₂), or        titania (TiO2);    -   the solvent being ultra pure water;    -   the inline blender being a static mixer;    -   the inline blender being a stirrer;    -   the inline blender being a vortex element;    -   the inline blender being a combination of a static mixer and a        vortex element;    -   downstream of the inline blender being a tube or pipe having an        unrestricted flow path;    -   downstream of the inline blender not being a mixing or holding        tank;    -   wherein Component A, Component B, and the solvent are mixed        together in one inline blender to form the mixture;    -   wherein Component A, Component B, the solvent, and the abrasive        particles are mixed together in one inline blender to form the        mixture;    -   maintaining the target concentration of Component A within        0.001% w/w;    -   maintaining the target concentration of Component B within        0.001% w/w;    -   Component A comprising species that affect the concentration of        Component B;    -   Component B comprising species that affect the concentration of        Component A;    -   the flow rate of Component A, Component B, and/or the solvent        being adjusted using a PID algorithm;    -   Component A being HF and Component B being NH₄F;    -   Component A being a slurry and Component B being H₂O₂    -   Component A being NH₄OH and Component B being H₂O₂;    -   Component A being HCl and Component B being H₂O₂;    -   Component A being H₂SO₄ and Component B being H₂O₂;    -   Component A being NH₄OH and Component B being ammonium acetate;    -   Component A being NaHCO₃ and Component B being NaOH;    -   analyzing the concentration of Component A using a different        analyzer than that used to measure the concentration of        Component B;    -   the concentration of Component A and the concentration of        Component B being monitored by a combination of a conductivity        meter, a pH meter, a refractometer, a turbidity monitor, a Raman        spectrometer, an infrared spectrometer, a UV/VIS spectrometer, a        densitometer, an ultra-sonic meter, and a particle counter;    -   the concentration of HF being determined using a pH meter;    -   the concentration of the slurry being determined by a        densitometer;    -   the concentration of H₂O₂ being determined by a refractometer;    -   the concentration of HCl being determined using a pH meter;    -   the concentration of HF being determined using a conductivity        meter;    -   the concentration of HCl being determined using a conductivity        meter;    -   the concentration of H₂SO₄ being determined using a conductivity        meter;    -   the concentration of NH₄F being determined using a conductivity        meter;    -   the concentration of NH₄OH being determined using a conductivity        meter;    -   the concentration of H₂O₂ being determined using a        refractometer;    -   adjusting the flow rate of Component A using a PID algorithm;    -   adjusting the flow rate of Component B using a PID algorithm;    -   the flow rate of HF being adjusted using a direct acting PID        algorithm; and    -   the flow rate of NH₄F being adjusting using a reverse acting PID        algorithm.

Methods of mixing chemical fluids in an inline blender to produce amixture having a concentration of the chemical fluids within 0.22% w/wof a target concentration are also disclosed. A first chemical fluid isintroduced into an inline blender via a first flow control device. Asecond chemical fluid is introduced into the inline blender via a secondflow control device. A third chemical fluid is introduced into theinline blender via a third flow control device. The first chemicalfluid, the second chemical fluid, and the third chemical fluid are mixedin a mixing zone of the inline blender to form a mixture. The mixture ismonitored downstream from the mixing zone for a first chemical fluidconcentration and a second chemical fluid concentration. The first flowcontrol device is adjusted based on the first chemical fluidconcentration. The second flow control device is adjusted based on thesecond chemical fluid concentration. The disclosed methods may includeone or more of the following aspects:

-   -   maintaining the target concentration notwithstanding the source        of the first chemical fluid and/or the second chemical fluid        and/or the third chemical fluid;    -   the first flow control device, the second flow control device,        and the third flow control device being an orifice, a flow        control valve, a stepper throttle, or combinations thereof;    -   the mixing zone being a tube or a pipe having an unrestricted        flow path;    -   the mixing zone comprising an element to induce mixing;    -   the element to induce mixing being a static mixer, a stirrer, a        vortex element, or combinations thereof;    -   downstream of the inline blender being a tube or pipe having an        unrestricted flow path;    -   downstream of the inline blender not being a mixing or holding        tank;    -   the mixture being a solution;    -   the mixture being a slurry;    -   the slurry comprising a basic solution;    -   the slurry comprising an acidic solution;    -   the slurry comprising abrasive particles;    -   the abrasive particles being silica (SiO₂), alumina (Al₂O₃),        calcium carbonate (CaCO₃), ceria (CeO₂), zirconia (ZrO₂), or        titania (TiO2);    -   wherein the first chemical fluid, the second chemical fluid, and        the third chemical fluid are mixed together in one mixing zone        of the inline blender to form the mixture;    -   maintaining the target concentration of the first chemical fluid        within 0.008% w/w;    -   maintaining the target concentration of the second chemical        fluid within 0.22% w/w;    -   the first chemical fluid and the second chemical fluid not being        water;    -   the first chemical fluid being H₂SO₄, HF, NH₄OH, or HCl;    -   the second chemical fluid being H₂O₂ or NH₄F;    -   the third chemical fluid being water;    -   the first chemical fluid being HF and the second chemical fluid        being NH₄F;    -   the first chemical fluid being NH₄OH and the second chemical        fluid being H₂O₂;    -   the first chemical fluid being HCl and the second chemical fluid        being H₂O₂;    -   the first chemical fluid being H₂SO₄ and the second chemical        fluid being H₂O₂;    -   the first chemical fluid being NH₄OH and the second chemical        fluid being ammonium acetate;    -   the first chemical fluid being NaHCO₃ and the second chemical        fluid being NaOH;    -   the first chemical fluid comprising ions that affect the second        chemical fluid concentration;    -   the second chemical fluid comprising ions that affect the first        chemical fluid concentration;    -   the ions being selected from H⁺, NH₄ ⁺, SO₄ ²⁻, F⁻, OH⁻, or Cl⁻;    -   the ions being selected from H⁺, NH₄ ⁺, H⁻, OH⁻, OOH⁻, O₂ ⁻, or        F⁻;    -   analyzing the concentration of the first chemical fluid using a        different analyzer than that used to measure the concentration        of second chemical fluid;    -   the first chemical fluid concentration and the second chemical        fluid concentration being monitored by a combination of a        conductivity meter, a pH meter, a refractometer, a turbidity        monitor, a Raman spectrometer, an infrared spectrometer, a        UV/VIS spectrometer, a densitometer, an ultra-sonic meter and a        particle counter;    -   the first chemical fluid concentration being monitored by a        temperature-adjusted conductivity meter;    -   the second chemical fluid concentration being monitored by a        temperature-adjusted pH meter;    -   the concentration of HF being determined using a pH meter;    -   the concentration of slurry being determined by a densitometer;    -   the concentration of H₂O₂ being determined by a refractometer;    -   the concentration of HCl being determined using a pH meter;    -   the concentration of HF being determined using a conductivity        meter;    -   the concentration of HCl being determined using a conductivity        meter;    -   the concentration of H₂SO₄ being determined using a conductivity        meter;    -   the concentration of NH₄F being determined using a conductivity        meter;    -   the concentration of NH₄OH being determined using a conductivity        meter;    -   the flow rate of H₂O₂ being adjusted using a refractometer;    -   adjusting the flow rate of the first chemical fluid using a PID        algorithm;    -   adjusting the flow rate of second chemical fluid using a PID        algorithm;    -   the flow rate of HF being adjusted using a direct acting PID        algorithm; and    -   the flow rate of NH₄F being adjusting using a reverse acting PID        algorithm.

Methods of mixing acids and bases in an inline blender to producemixtures having consistent concentrations are also disclosed. A solventis introduced into an inline blender via a first flow control device. Anacid is introduced into the inline blender via a second flow controldevice. A base is introduced into the inline blender via a third flowcontrol device. The acid, base, and solvent are mixed in a mixing zoneof the inline blender to form a mixture. The mixture is monitoreddownstream from the mixing zone for an acid concentration and a baseconcentration. The second flow control device is adjusted based on theacid concentration. The third flow control device is adjusted based onthe base concentration. The disclosed methods include one or more of thefollowing aspects:

-   -   maintaining the acid concentration and the base concentration        notwithstanding the source of the acid and/or the base;    -   the first flow control device, the second flow control device,        and the third flow control device being an orifice, a flow        control valve, a stepper throttle, or combinations thereof;    -   wherein the acid, base, and solvent are mixed together in one        mixing zone of the inline blender to form the mixture;    -   the mixing zone being a tube or a pipe having an unrestricted        flow path;    -   the mixing zone comprising an element to induce mixing;    -   the element to induce mixing being a static mixer, a stirrer, a        vortex element, or combinations thereof;    -   downstream of the mixing zone being a tube or pipe having an        unrestricted flow path;    -   downstream of the mixing zone not being a mixing or holding        tank;    -   the mixture being a solution;    -   monitoring the acid concentration using a different analyzer        than that used to measure the base concentration;    -   the acid concentration and base concentration being monitored by        a combination of a conductivity meter, a pH meter, a        refractometer, a turbidity monitor, a Raman spectrometer, an        infrared spectrometer, a UV/VIS spectrometer, a densitometer, an        ultra-sonic meter and a particle counter;    -   maintaining the target concentration of the acid within 0.01%        w/w;    -   maintaining the target concentration of the base within 0.01%        w/w;    -   maintaining the target concentration of the acid within 0.001%        w/w;    -   maintaining the target concentration of the base within 0.001%        w/w;    -   the solvent being water;    -   the acid and the base not being water;    -   the acid comprising ions that affect the base concentration;    -   the acid being HF;    -   the ions being selected from the group consisting of H⁺ and F⁻;    -   the base comprising ions that affect the acid concentration;    -   the base being NH₄F;    -   the ions being selected from the group consisting of H⁺, NH₄ ⁺,        H⁻, or F⁻;    -   the base concentration being monitored by a        temperature-compensated conductivity meter; and    -   the acid concentration being monitored by a        temperature-compensated pH meter.

Methods of mixing an oxidizer and a reducer in an inline blender toproduce a mixture having a consistent concentration are also disclosed.A solvent is introduced into an inline blender via a first flow controldevice. An oxidizer is introduced into the inline blender via a secondflow control device. A reducer is introduced into the inline blender viaa third flow control device. The oxidizer, reducer, and solvent aremixed in a mixing zone of the inline blender to form a mixture. Themixture is monitored downstream from the mixing zone for an oxidizerconcentration and a reducer concentration. The second flow controldevice is adjusted based on the oxidizer concentration. The third flowcontrol device is adjusted based on the reducer concentration. Thedisclosed methods may include one or more of the following aspects:

-   -   maintaining the oxidizer concentration and the reduce        concentration notwithstanding the source of oxidizer and/or the        reducer;    -   the first flow control device, the second flow control device,        and the third flow control device being an orifice, a flow        control valve, a stepper throttle, or combinations thereof;    -   wherein the oxidizer, reducer, and solvent are mixed together in        one mixing zone of the inline blender to form the mixture;    -   the mixing zone being a tube or a pipe having an unrestricted        flow path;    -   the mixing zone comprising an element to induce mixing;    -   the element to induce mixing being a static mixer, a stirrer, a        vortex element, or combinations thereof;    -   downstream of the mixing zone being a tube or pipe having an        unrestricted flow path;    -   downstream of the mixing zone not being a mixing or holding        tank;    -   the mixture being a solution;    -   monitoring the oxidizer concentration using a different analyzer        than that used to measure the reducer concentration;    -   the oxidizer concentration and reducer concentration being        monitored by a combination of a conductivity meter, a pH meter,        a refractometer, a turbidity monitor, a Raman spectrometer, an        infrared spectrometer, a UV/VIS spectrometer, a densitometer, an        ultra-sonic meter and a particle counter;    -   maintaining the target concentration of the oxidizer within        0.01% w/w;    -   maintaining the target concentration of the reducer within 0.01%        w/w;    -   maintaining the target concentration of the oxidizer within        0.001% w/w;    -   maintaining the target concentration of the reducer within        0.001% w/w;    -   the solvent being water;    -   the oxidizer and the reducer not being water;    -   the oxidizer comprising ions that affect the reducer        concentration;    -   the oxidizer being H₂O₂ or NH₄OH;    -   the ions being H⁺, NH₄ ⁺, or OH⁻;    -   the reducer comprising ions that affect the oxidizer        concentration;    -   the reducer being H₂O₂, H₂SO₄, or HCl;    -   the ions being H⁺, H⁻, OH⁻, OOH⁻, O²⁻, HSO4⁻, SO4²⁻, or Cl⁻;    -   monitoring the reducer concentration by a        temperature-compensated conductivity meter; and    -   monitoring the oxidizer concentration by a        temperature-compensated pH meter.

An inline chemical blender for mixing chemicals in real-time is alsodisclosed. Three chemical fluid flow control devices communicate threechemical fluids from their sources to a mixing zone of the inlinechemical blender. Three sensors are located downstream of the mixingzone, one of which monitors the temperature of the mixture and two ofwhich measure the concentrations of two of the chemical fluids in themixture. The disclosed inline chemical blender may include one or moreof the following aspects:

-   -   each flow control device being an orifice, flow control valve,        stepper throttle, or combinations thereof;    -   the mixing zone being a tube or pipe;    -   the mixing zone being a tank or reservoir;    -   downstream of the mixing zone being a tube or pipe having an        unrestricted flow path;    -   downstream of the mixing zone not being a mixing or holding        tank;    -   measuring the concentration of a first chemical fluid using a        different sensor than that used to measure the concentration of        a second chemical fluid;    -   maintaining a concentration of the first chemical fluid in the        mixture and a concentration of the second chemical fluid in the        mixture notwithstanding the source of the first chemical fluid        and/or the second chemical fluid;    -   the sensors being combinations of a temperature sensor, a        conductivity meter, a pH meter, a refractometer, a turbidity        monitor, a Raman spectrometer, an infrared spectrometer, a        UV/VIS spectrometer, a densitometer, an ultra-sonic meter and a        particle counter;    -   the sensors communicating with the flow control devices via a        PID algorithm;    -   the PID algorithm adjusting the flow rate of a chemical fluid        proportionally to the pH results of the chemical fluid;    -   the PID algorithm increasing the flow rate of a chemical fluid        when the pH results of the chemical fluid increase;    -   the PID algorithm adjusting the flow rate of a chemical fluid        inversely to the conductivity results of the chemical fluid;    -   the PID algorithm decreasing the flow rate of a chemical fluid        when the conductivity results of the chemical fluid increase;        and    -   further comprising a drain downstream of the mixing zone.

BRIEF DESCRIPTION OF THE DRAWINGS

For a further understanding of the nature and objects of the presentinvention, reference should be made to the following detaileddescription, taken in conjunction with the accompanying drawings, inwhich like elements are given the same or analogous reference numbersand wherein:

FIG. 1 is a block schematic diagram of a prior art inline blender;

FIG. 2 is a graph showing concentration (wt. %) versus conductivity(mS/cm) of two blend points produced by the prior art inline blender ofFIG. 1;

FIG. 3 is a block schematic diagram of an inline blender with a proposedoffline chemical analysis feedforward step;

FIG. 4 is a block schematic diagram of the disclosed inline blender;

FIG. 5 is a graph showing pH versus HF concentration for differentmolarity NH₄F solutions; and

FIG. 6 is the graph demonstrating how to select the pH and conductivityset points necessary to produce the blend having the desiredconcentration, notwithstanding the assay of the source materials.

DESCRIPTION OF PREFERRED EMBODIMENTS

Inline blending multiple chemical constituents in a way that is accurateand repeatable is difficult when the chemical constituents interact withand affect each other. Even if the assay of each chemical constituentconsistently remains within a specification window, the effect ofcompounding error may make it difficult to control the specification forthe final blended product.

The prior art volume-based and weight-based blending processes do notaddress this issue, since they depend solely on the known specificationof the incoming material.

Metrology-based feedback inline blenders use techniques such asconductivity, pH, refractive index, density, turbidity, and othermeasurements, in order to control the flow rate of the chemicals andmaintain the final blended material specification.

Previous continuous inline blenders, of the type schematicallyrepresented in FIG. 1, have a series of “Blend Points” with oneconstituent species added at each blend point and controlled locallywith a feedback metrology device, typically conductivity, but alsoRefractive Index, pH, Ultra Sonic, densitometers, etc. The firstcomplication to final blend accuracy in these series of continuousinline blenders arises at the second blend point. The concentration ofthe first blend point is immune to the single species source assay, suchas 49% HF acid, because the first series blend point with feedbackprovides for the correct first blend point assay even if the chemicalsource is 48% HF acid. The feedback from the first blend point allowsmore flow of the 48% HF source to compensate. However, the secondblendpoint is not immune to the single species source assay, even whenthe second chemical source is a single species, such as NH₄F having noother added species, such as HF or NH₃. if the single species NH₄Fsource assay varies from the expected 40% NH₄F w/w (e.g., 39% or 41%NH₄F w/w), the variance ripples upstream and alters the intended assayof the first blend point by diluting or concentrating it. In otherwords, the addition of the second chemical having an assay that differsfrom expected results in an improper concentration of the first chemicalin the final solution.

Concentration control is further impacted when the two chemicalcompounds to be blended alter each other's concentrations. In otherwords, prior art systems use of subsequent sensors to measure theconcentration of each sequentially added component fails to address theimpact a subsequent component may have on the concentration of anearlier component. As a result, some solutions cannot be blended withoutambiguous output based upon the prior art single component/single sensorembodiment. For example, any traces of NH₃ or HF in NH₄F may negativelyaffect the total HF concentration in a buffered oxide etch solution.

A term used to describe the robustness of a blender for source chemicalconcentrations is “Source Immunity”. This describes the level to whichthe final inline blend concentration target can be maintained withvariations in the concentration of the input source chemicals. SingleSpecies Source Immunity exists only at the first blend point. In otherwords, the final output of the blending with feedback from aconductivity signal for simple HF dilution blending is immune to theinput HF concentration (i.e., 48% wt/wt, 49% wt/wt, 46% wt/wt, etc.).

For each subsequent series blend point (i.e., second, third, etc.), theprecise source assay input must be known and constant, or concentrationor dilution of the first constituent may take place and result in an outof specification assay condition for the first component at the secondand/or third blend points. This type of blend error ripples upstreamthrough the series of continuous inline blenders. The second componentmay be out of specification at the third and fourth blend points.

This continuous inline blender limitation is worsened when certainspecies are present in more than one of the chemical constituents beingblended. For example, NH₄F may include H₂O, OH⁻, NH₄F, NH₃, NH₄ ⁺, HF,H⁺, and F⁻. When HF and NH₄F are blended, any HF or F— present thereinmay alter the concentration of HF in the final blend.

In the semiconductor industry, due to the high purity required for thechemicals and blends containing these chemicals, gas phase generation ofthe chemical or blend is typical and preferable compared to simple solidphase dissolution of various salts etc. As a result, the final assay mayalso include free species in the gas phase due to difficulty controllingthe final gas phase end point.

When multiple chemicals are blended, for example deionized water(DIW)+Chemical A+Chemical B, the prior art teaches that Chemical A isadded at a first chemical mixing zone, controlled by a first metrologyfeedback, and Chemical B is added sequentially into a second chemicalmixing zone, controlled by a second metrology feedback. See, e.g., U.S.Pat. No. 6,050,283 to Air Liquide America Corp. Additional chemicaladditions are possible, each one added in sequence with a dedicatedmetrology feedback control. When the incoming source materialspecification changes, the blender described above is not able to detector correct for that condition for all upstream chemicals, and theblended material may be out of specification.

Accurate mixing of chemicals is particularly important in at least thesemiconductor industry due to the continuous shrinking of the productsize necessitated by Moore's law. Failure to maintain the specifiedconcentrations may introduce product variations or even failure. Productdegradation may occur when the product is shipped from off-site or if abatch sits for too long.

Buffered chemical solutions using salt buffers are particularlyafflicted by the limitations of the prior art continuous inlineblenders. For example, many buffered oxide etch formulations will use anammonium fluoride (i.e., NH₄F) salt buffer to create a bufferedhydrofluoric acid solution for etch control. The original NH₄F solutionis manufactured by dissolving NH₃ gas into a hydrofluoric acid solutionand attempting to stop the manufacturing process at the neutral point(i.e., the point at which there is no excess HF or NH₃ in the solution).If the reaction is stopped too early, the final ammonium fluoridebecomes HF rich and if the reaction is stopped late, the resultingammonium fluoride would be NH₃ rich. Alternatively, the entire ammoniumfluoride salt buffer may be generated from the gas phase by firstdissolving anhydrous HF into water to form HF acid and then dissolvingNH₃ gas into the HF acid to formulate the ammonium fluoride. In thiscase, if the reaction is stopped too early, the final ammonium fluoridebecomes HF rich and if the reaction is stopped late, the resultingammonium fluoride would be NH₃ rich. As a result, the final blend assayis affected by the unknown and non-constant free species in the ammoniumfluoride source material.

Preparation of a buffered oxide etch solution is described as followsusing a typical prior art blender shown in FIG. 1 in block schematicform. In FIG. 1, Ultrapure Water, or UPW, 100 is blended with 49% w/w HF200 at blendpoint 250 to produce dilute HF. The UPW 100 may be deliveredto blendpoint 250 using a flow meter (not shown). The HF 200 may bedelivered to blendpoint 250 using a proportioning valve (not shown). Theproportioning valve (not shown) may deliver more or less HF 200 to theblendpoint 250 based on temperature corrected conductivity feedback 251to achieve the desired dilute HF assay. The dilute HF produced atblendpoint 250 is at the desired concentration independent of the actualHF 200 source assay (i.e., source immunity).

The dilute HF produced at blendpoint 250 is then blended with ammoniumfluoride 300, which may contain free NH₃ or HF, at blendpoint 350 toproduce the buffered oxide etch solution 400. Although depicted as a“block” in FIG. 1, one of ordinary skill in the art will recognize thatthe buffered oxide etch solution 400 is delivered either directly to theprocessing equipment or to a drain. The ammonium fluoride 300 may bedelivered to blendpoint 350 using a proportioning valve (not shown).

At blendpoint 350, the first general error may arise as a function ofthe actual ammonium fluoride assay—40.0%+/−1% NH₄F by wt. If this assayis not known and held constant across all sources of ammonium fluoride300, the HF assay in the buffered oxide etch solution 400 may be forcedout of specification. In addition, the final HF concentration may beaffected by the unknown and non-constant free species, NH₃ or HF,existing in the gas phase production generation of ammonium fluoridesource material 300. The final free HF assay in the buffered oxide etchsolution 400 typically requires a very high tolerance due to thesensitive process in which the etch solution is used.

As a result, the buffered oxide etch solution 400 only producesacceptable HF assays for one exact and specific assay of the ammoniumfluoride source material 300, for example 40.0% NH₄F and 0.05% Free HFby wt. Every time a new lot of ammonium fluoride 300 is brought onlineor if the ammonium fluoride 300 undergoes any changes in concentrationwhile being used, the blender set points must be changed to produce therequired buffered oxide etch solution assays. The ammonium fluorideassay may be performed using titration, functional silicon wafer etchtests, or a combination of both, all of which are time consuming andtime sensitive.

The UPW 100, HF 200, and NH₄F 300 are retrieved from industry standardstorage units. The storage units are in fluid communication withblendpoint 250 and 350. Blendpoint 250 and 350 are in fluidcommunication with a drain (not shown) and processing equipment (notshown). More particularly, supply lines supply the UPW 100, HF 200, andNH₄F 300 to the blendpoints 250 and 350. Similarly, supply lines supplythe resulting buffered oxide etch solution to a drain (not shown) orprocessing equipment (not shown). The supply lines are industry standardsupply lines. The supply lines may include flow control devices, such asorifices, flow control valves, stepper throttles, or combinationsthereof; valves, such as check valves or electronic valves; and/orpressure regulators.

Blendpoint 250 or 350 is a mixing zone, also known as an inline blender.The mixing zone may be a tube or pipe having an unrestricted flow path.Alternatively, the mixing zone may be a T junction. In eitheralternative, the tube or pipe may include an element to induce mixing,such as a static mixer, a stirrer, a vortex element, or combinationsthereof. One of ordinary skill in the art will recognize that thesuitable mixing zone will be determined based upon both the mixingconditions required and pressure necessary at the point of use. Moreparticularly, a viscous solution or slurry may require more forcefulmixing than a flowing solution and, as a result, an element to inducemixing. However, an element to induce mixing may result in loss ofpressure across the system. One of ordinary skill in the art willrecognize the mixing zone necessary based on equipment setup and theproduct to be mixed.

The supply line downstream of blendpoint 250 or 350 includes a sensor(not shown) that measures a characteristic of the blend. Exemplarysensors include conductivity meters, pH meters, refractometers,turbidity monitors, Raman spectrometers, infrared spectrometers, adensitometer, an ultra-sonic meter, spectrometers, and particlecounters. The sensors provide real-time feedback (i.e., 251, 351) to therelevant flow control device and adjusts the flow rate based on theanalysis results. For example, if the conductivity is a little high, aconductivity meter may instruct the flow control device for HF 100 todecrease the flow rate. If the conductivity is too high so that theresulting buffered oxide etch solution 400 is unusable, the sensor mayinstruct a valve in the line to divert the solution to the drain. Thesensors and flow control devices may communicate via a controller. Thecommunication may occur via electrical wiring or wireless communicationlinks. The controller may include a processor that is programmable toimplement any one or more suitable types of process control, such asproportional-integral-derivative (PID) feedback control. Exemplarycontrollers include the PLC Simatic S7-300 system from Siemens Corp.Also commonly used are Allen Bradley CompactLogix PLC Control and theAllen Bradley RSLogix programming suite.

Surprisingly, Applicants have found that neither the refractometer northe conductivity meter were capable of determining the concentration offree species in the resulting buffered oxide etch solution. However, pHanalysis properly reflects free species in the solution.

FIG. 2 is a graph that illustrates the resulting two blend pointoperating curve that demonstrates the inadequacy of the prior art inlineblender of FIG. 1. The graph shows the conductivity (in mS/cm) versusconcentration (in wt. %) of two blend points: 250 and 350. Point 250provides the concentration and conductivity of the solution atblendpoint 250 in FIG. 1, more particularly, 0.08% w/w HF and 3.300mS/cm. Point 350 provides the concentration and conductivity of thesolution from blendpoint 350 in FIG. 1, more particularly, 14.8% w/wNH₄F and 160 mS/cm. The operating curve shown in FIG. 2 is only validfor one unique ammonium fluoride source 300 assay. To obtain thebuffered HF 400 having 14.8% wt. NH₄F and 0.08% wt. HF from a HF 200source and an ammonium fluoride source 300 of 40% NH₄F by wt. and 0.000%free species, the blendpoint 250 is set to 3.300 mS/cm and the HF isadded from source HF 200 until a conductivity of 3.300 mS/cm is reachedat blendpoint 250. NH₄F is then added from source NH₄F 300 at blendpoint350 to a conductivity of 160 mS/cm. If the ammonium fluoride source 300changes, the 3.300 mS/cm setting at blendpoint 250 will no longer bevalid to obtain the final required buffered HF 400 solution. A uniqueblendpoint 250 must be found for every ammonium fluoride source 300assay as explained above.

Various techniques were tested to try to minimize or remove thisammonium fluoride assay dependence, including reversing the blend orderto blend ammonium fluoride first followed by HF, all unsuccessfully,because there is no method of compensating for the varying assays of theNH₄F source material using the blender arrangement of FIG. 1.

Based on the limitations of the prior art continuous inline blender ofFIG. 1, a “Feedforward” step was proposed that includes the assay of theammonium fluoride 300 and the amount of free species NH₃ or HF to alterthe setpoint for HF source at the blendpoint 250 analysis. A blockschematic of this proposal is shown in FIG. 3. An automated means (notshown) provides the concentration of free species and ammonium fluoridein the ammonium fluoride source 300 to blendpoint 250 as indicated bythe feedforward step 352. The automated means must remain accurate forthe NH₄F assay as well as free species NH₃ or HF across a full domain ofsource 300 input possibilities, pH for example, vs. just one singlevalue—the final disclosed blender setpoint. Based on mass balanceinformation and calculations, the new setpoint 352 was sent to theblendpoint 250. Various automated metrology devices were explored toprovide this automated solution, including conductivity, refractiveindex and pH. Due to mass balance offsets, convoluted intermediate stepswith errors, and difficulty obtaining the true assay of the ammoniumfluoride 300, not to mention the long time interval, consumables andequipment costs necessary to run such an automated analytical assayprocess, this proposal was rejected. Blendpoint 350 of FIGS. 2 and 3must remain fixed because the final buffered oxide etch solution 400assay must be fixed.

FIG. 4 is a block schematic of the inline blender that solves theproblems that have not been resolved in the prior art. As will bedescribed in more detail below, blendpoint 250 of FIGS. 1 and 3 has beeneliminated and blendpoint 350 now provides temperature compensated pHfeedback 251 to the proportioning valve (not shown) for HF 200 andtemperature compensated conductivity feedback 351 to the proportioningvalve (not shown) for the ammonium fluoride source 300.

Chemical equilibrium arises within a buffering salt and acid. Asdiscussed above for the buffered oxide etch solution, using NH₄F as thesalt buffer results in the following chemical solution species:

-   -   H₂O (I)    -   HF (aq)    -   H⁺    -   OH⁻    -   NH₄ ⁺    -   NH₃    -   F⁻        In FIG. 4, the NH₄F salt is fully dissolved in the aqueous        solution at NH₄F source 300. The pH feedback 251 and        conductivity feedback 351 must take place after complete mixing        of UPW 100, HF 200, and NH₄F 300 (i.e., completion of any        chemical reaction, salt formation from NH₃ rich material, etc.)        and establishment of a full chemical equilibrium for all the ion        species.

At chemical equilibrium, an Initial, Change, Equilibrium (“ICE”) matrixfor the components to be reacted may be established to determine thesensor settings needed. Alternatively, for many cases, the shortcutHenderson-Haselbalch equation may be used (i.e., pH=pK_(a)+log₁₀([A−]/[HA]), wherein K_(a) is the acid dissociation constant, [HA] isthe molar concentration of the un-dissociated weak acid, and [A−] is themolar concentration of the conjugate base of HA). One of ordinary skillin the art will recognize that the ICE matrix or Henderson-Haselbachequations are temperature dependent.

The resulting chemical operating curve is shown in FIG. 5, which is agraph showing pH of the blend versus HF molar concentration fordifferent molarity NH₄F solutions. The FIG. 5 graph shows a family ofcurves representing the molarity of the salt buffer NH₄F. 10 curves areshown for NH₄F molarity ranging from 0.5 M to 5.0 M. The molarity of theNH₄F buffer solution provides the desired conductivity reading. Forexample, the solid line represents 0.5 M NH₄F; the dotted linerepresents 1.0 M NH₄F; the triangled line represents 1.5 M NH₄F; thesquared line represents 2.0 M NH₄F; the dot-dash line represents 2.5 MNH₄F; the dashed line represents 3.0 M NH₄F; the dot-dot-dash linerepresents 3.5 M NH₄F; the circled line represents 4.0 M NH₄F; the

line represents 4.5 M NH₄F; and the diamond line represents 5.0 M NH₄F.Data of concentration versus conductivity for various chemicals arepublished at 25° C. For each molarity of NH₄F above, a specifictemperature compensated conductivity is manifested. For highest accuracyin the disclosed blender, the actual temperature compensatedconductivity at each salt buffer concentration is determinedempirically.

Each NH₄F molarity curve intersects the pH and HF concentration axes atdifferent points. As shown by the solid graph grid line at pH=4.5, aconstant pH may be maintained with increasing HF concentration due tothe buffering effect obtained by the increasing NH₄F M. The desiredconcentration of the oxide etch buffer solution may be selected todetermine the needed molarity/conductivity of the NH₄F and pH of theresulting oxide etch buffer solution. For example, as shown in FIG. 6,if the desired blend contains 14.8% NH₄F by wt. (4.00 M or 160.00 mS/cm)and 0.08000% HF by wt (0.04 M), the resulting pH is 5.1. The resultingsetpoints for the blender sensors using this example are:

-   -   Temperature Compensated Conductivity 351=160.00 mS/cm    -   Temperature Compensated pH 251=5.1

Instead of a cascaded series of inline blend points used by thetraditional continuous blender, just one blend point 350 may be used asthe confluence of all the constituents, and feedback is established toobtain the setpoints from the operating curve shown in FIG. 5. As aresult, the blender occupies a smaller footprint than the prior artmulti-blend point inline blender and further may require lessmaintenance.

Experimentation in a full scale blender has demonstrated that usingconventional proportional-integral-derivative (PID) feedback control,final blend output assay control is automatically, (via the disclosedPID feedback control), obtained/maintained, regardless of HF or NH₄Fsource assays. The conventional PID feedback control system is anelectronic closed-loop control between the flow meters, control valves(or pump control), and analyzers. The analyzer results are used toadjust the flow meters and/or control valves in order to maintain thefinal desired blend assay.

The NH₄F Molarity/Concentration is automatically controlled with a“Reverse Acting”, (SP-PV), traditional PID algorithm—as conductivityrises, NH₄F flow drops via the PID algorithm.

The HF Molarity/Concentration is automatically controlled with a “DirectActing”, (PV-SP), traditional PID algorithm—as pH rises, HF flowincreases via PID algorithm.

These two automatic PID feedback algorithms ensure the final blendoutput is at the temperature compensated conductivity and temperaturecompensated pH and therefore at the unique and required blend outputassay.

When a new NH₄F source is placed online, regardless of the NH₄F assay orthe amount of free NH₃ or HF, final blend assay is controlled byautomatically via the PID feedback as explained above to maintain thedesired conductivity and pH and thus the final stable and consistentNH₄F and HF assay. The final blend does not change as a function of theorigin of the free HF species—either in the HF source or the NH₄F sourceas long as the six species alone are present, mixing is complete,chemical equilibrium is established, and process variables aretemperature compensated as discussed previously. Nor does the bulkconcentration of salt in the source NH₄F effect the final blend assay,but instead simply by the flow of NH₄F driven from the Reverse ActingPID algorithm.

The resulting solutions/slurries having the desired concentration may beprepared on-demand without worrying about any changes to theconcentrations of the starting materials. More particularly, thedisclosed methods produce solutions and slurries on demand that are ableto maintain concentrations within 0.22% w/w of the desiredconcentration. Depending on the chemical and measuring technique, theconcentration may be maintained within 0.008% w/w of the desired goal.As shown in the examples that follow, this is an improvement over theresults obtained using the prior art blender of FIG. 1.

While tests to date have been performed using the buffered oxide etchsolution (i.e., NH₄F/HF/H₂O), Applicants believe that the disclosedblending process may also be used for other solutions requiring highprecision that are common in the electronics industry including, but notlimited to, solutions such as NH₄OH/H₂O₂/H₂O, HCl/H₂O₂/H₂O, orH₂SO₄/H₂O₂/H₂O or slurries containing abrasive particles, such as silica(SiO₂), alumina (Al₂O₃), calcium carbonate (CaCO₃), ceria (CeO₂),zirconia (ZrO₂), or titania (TiO2) in a basic solution such asNH₄OH/ammonium acetate/H₂O or NaHCO₃/NaOH/H₂O or an acidic solution suchas NH₄F/HF/H₂O.

EXAMPLES

The following non-limiting examples are provided to further illustrateembodiments of the invention. However, the examples are not intended tobe all inclusive and are not intended to limit the scope of theinventions described herein.

Disclosed Blender Example

The inline blender of FIG. 4 was built in the research laboratory todetermine whether the final concentration was maintained after changingNH₄F source 300. Due to the research settings and waste managementrequirements, the concentrations in these examples are less thantypically encountered in the industry.

The trial runs were performed with an Ultra Pure Water (UPW) flow rateof 1.75 liters per minute (Lpm) flowing from UPW source 100. A pH probeand conductivity probe for feedback elements 251 and 351 was added afterblendpoint 350. A PTFE six stage static mixer purchased from Edlon Inc.was used for blendpoint 350.

Each Feedback Metrology Subsystem was tuned and optimized for this UPWflow rate for maximum stability/response. This was accomplished usingthe resident onboard Allen Bradley CompactLogix PLC Control and theAllen Bradley RSLogix programming suite using the PIDE(Proportional-Integral-Derivative Enhanced) Function Block.

The AutoTune feature of the PIDE Function Block was used to tune the PIDparameters for optimum operation at the setpoints of Conductivity=50.00mS/cm, pH=5.50. These AutoTune deduced PID parameters were rounded offand used for the Deterministic Blend Runs.

The following parameters were set:

Parameter Description Parameter Value Units UPW Blender Flow Rate 1750mL/min NH₄F Conductivity 0.0183 ° C.⁻¹ Temperature Compensation Alpha pHInstrumentation Endress and Hauser No units Temperature Auto TempCompensation Compensation NH₄F PIDE Feedback Parameters PID EquationType Independent Control Action Reverse Acting SP-PV No units LoopUpdate Time 100 Milliseconds Deadband 0.0 K_(p) 0.4 unitless K_(i) 3.6minutes⁻¹ K_(d) 0.007 minutes HF PIDE Feedback Parameters PID EquationType Independent Control Action Direct Acting PV-SP No units Loop UpdateTime 100 milliseconds Deadband 0.0 K_(p) 20 unitless K_(i) 80.0minutes⁻¹ K_(d) 0.4 minutes

To prepare for the experimental runs of the disclosed blender, threesource containers of chemical were prepared:

-   -   1. Source 200 was 49% HF    -   2. Source 300 supply #1 contained 40% NH₄F w/w and neutral free        species, i.e. no free NH₃ or HF    -   3. Source 300 supply #2 contained 40% NH₄F w/w and 0.9% free HF        w/w

The second HF rich source 300 was designed to challenge the system incomparison to the neutral free species source 300 supply #1 and for thesystem to throttle back the amount of HF delivered to the blend viasource 200 and maintain the same final blend as more HF is delivered viasource 300 supply #2. As a result, the concentrations of the firstsource 300 supply #1 will be considered the desired concentration.

At the end of this full scale blender test cycle, samples of the blenderoutput were collected and retained and titrated for HF and NH₄F assaywith a Mettler Toledo Excellence T70 Titrator. External measurements ofthe conductivity and the pH were also measured in a beaker using:

-   -   Mettler Toledo InLab 717 Conductivity Probe    -   Calibrated with a 12.9 mS/cm conductivity standard.    -   Mettler Toledo DG111-SC pH Probe    -   Calibrated using 5.00 and 8.00 pH standards.

The results of the two output blends from the disclosed blender FIG. 4are shown in the table below: Both disclosed Deterministic Blend samplesblended with source 200 HF 49% w/w.

External Measured External NH₄F Sample Conductivity Measured HF AssayAssay Description (mS/cm) pH (% w/w) (% w/w) Source 300 50.7494 5.2780.1655 2.7030 Supply #1 40% NH₄F w/w 0.00% free HF w/w 0.00% free NH₃Source 300 50.8206 5.247 0.1675 2.6881 Supply #2 40% NH₄F w/w 0.90% freeHF w/w 0.00% free NH₃F Assay change +0.0020 −0.0149 (% w/w) Accuracy = %Assay 1.2% 0.56% composition change = (Assay change/ initial result) ×100

As can be seen, the system maintained the concentration of HF within+0.0020% w/w and NH₄F within −0.0149% w/w in the final productnotwithstanding the change of NH₄F source 300. These results are wellwithin the claimed concentration limits. Using the targeted temperaturecompensated pH and conductivity, a final product assay with smallvariations was achieved. In addition, these results were obtained onsmall volume samples, and do not benefit from the long term averagingthat continuous dynamic blending provides. As a result, when implementedinto a single blend point configuration and using two control loops forthe different feeds, a much tighter control on the variation of thetargeted pH and conductivity is expected. The tighter control on thesecritical control parameters will lead to a much tighter control on thefinal product assay notwithstanding variations in the feed productassay.

Prior Art Example

In order to contrast the blend output result from the prior art blenderof FIG. 1, a series blender with two blend points with conductivityfeedback as in FIG. 2 was simulated. Blendpoint 250 was reproduced in alarge beaker with dilute HF to a conductivity of 50 mS/cm as measured bythe same external conductivity probe as in the example above, a MettlerToledo InLab 717 Conductivity Probe. The sample was split into two smallbeakers. In one beaker, source 300 supply #1 was added to a conductivityof 50 mS/cm and in the other beaker, source 300 supply #2 was added to aconductivity of 50 mS/cm; this is the series operation of the prior artblender with conductivity feedback. The two beakers were then titratedwith the same Mettler Toledo Excellence T70 Titrator as in the exampleabove to obtain the HF assay. The conductivity and pH were measured withthe Mettler Toledo InLab 717 Conductivity Probe and the Mettler ToledoDG111-SC pH Probe in the same way as was done in the example above.

The results of the two output blends from the prior art blendersimulation of FIG. 1 are shown in the table below:

External Measured External NH₄F Sample Conductivity Measured HF AssayAssay Description (mS/cm) pH (% w/w) (% w/w) Source 300 49.436 4.9080.1751 Not Supply #1 measured 40% NH₄F w/w 0.00% free HF w/w 0.00% freeNH₃ Source 300 49.256 4.795 0.2661 Not Supply #2 measured 40% NH₄F w/w0.90% free HF w/w 0.00% free NH₃F Assay change +0.0910 N/A (% w/w)Accuracy = % Assay +51.97% N/A composition change

As can be seen, the HF assay alone is more than 10 times larger than theclaimed target concentration window (i.e., ±0.008% w/w). As a result,the two exemplary blend output tables confirm the essence of thedisclosed invention; that the Deterministic Blender can compensate forchanges to NH₄F source 300, where the prior art is blind and unable toadjust to the changing source 300 levels of free HF. Neither of theseexamples take advantage of the inherent benefits of dynamic blending,which generally leads to a tighter control on the targeted final blendcontrol characteristics i.e., pH and conductivity. The disclosedprocesses simply provide a means of having the correct target for theconductivity and pH without concern for the feed assay.

It will be understood that many additional changes in the details,materials, steps, and arrangement of parts, which have been hereindescribed and illustrated in order to explain the nature of theinvention, may be made by those skilled in the art within the principleand scope of the invention as expressed in the appended claims. Thus,the present invention is not intended to be limited to the specificembodiments in the examples given above and/or the attached drawings.

We claim:
 1. An inline blending method of components that alter each other's assays, the method comprising: a. mixing Component A, Component B, and a solvent in an inline blender to form a mixture; b. analyzing the mixture downstream of the inline blender to determine a concentration of Component A and a concentration of Component B; c. maintaining a target concentration in the mixture of Component A within 0.008% w/w and maintaining a target concentration in the mixture of Component B within 0.22% w/w by adjusting a flow rate of Component A, Component B, and/or the solvent based on the concentration of Component A and the concentration of Component B.
 2. The inline blending method of claim 1, wherein the solvent is ultra purified water.
 3. The inline blending method of claim 2, wherein Component A comprises species that affect the concentration of Component B.
 4. The inline blending method of claim 2, wherein Component B comprises species that affect the concentration of Component A.
 5. The inline blending method of claim 4, wherein Component A is HF and Component B is NH₄F.
 6. The inline blending method of claim 2, wherein Component A is NH₄OH and Component B is H₂O₂.
 7. The inline blending method of claim 2, wherein Component A is HCl and Component B is H₂O₂.
 8. The inline blending method of claim 2, wherein Component A is H₂SO₄ and Component B is H₂O₂.
 9. A method of mixing chemical fluids in an inline blender to produce a mixture having a concentration of the chemical fluids within 0.22% w/w of a target concentration, the method comprising: a. introducing a first chemical fluid into an inline blender via a first flow control device; b. introducing a second chemical fluid into the inline blender via a second flow control device; c. introducing a third chemical fluid into the inline blender via a third flow control device; d. mixing the first chemical fluid, the second chemical fluid, and the third chemical fluid in a mixing zone of the inline blender to form a mixture; e. monitoring the mixture downstream from the mixing zone for a first chemical fluid concentration and a second chemical fluid concentration; f. adjusting the first flow control device based on the first chemical fluid concentration; and g. adjusting the second flow control device based on the second chemical fluid concentration.
 10. The method of claim 9, wherein the first flow control device, the second flow control device, and the third flow control device is an orifice, a flow control valve, a stepper throttle, or combinations thereof.
 11. The method of claim 9, wherein the mixing zone is a tube or a pipe having an unrestricted flow path.
 12. The method of claim 9, wherein the mixing zone comprises an element to induce mixing.
 13. The method of claim 12, wherein the element to induce mixing is a static mixer, a stirrer, a vortex element, or combinations thereof.
 14. The method of claim 9, wherein the first chemical fluid concentration and the second chemical fluid concentration are monitored by combinations of a conductivity meter, a pH meter, a refractometer, a turbidity monitor, a Raman spectrometer, an infrared spectrometer, a UV/VIS spectrometer, a densitometer, an ultra-sonic meter, and a particle counter.
 15. The method of claim 9, wherein the first chemical fluid and the second chemical fluid are not water.
 16. The method of claim 9, wherein the first chemical fluid is H₂SO₄, HF, NH₄OH, or HCl.
 17. The method of claim 9, wherein the second chemical fluid is H₂O₂ or NH₄F.
 18. The method of claim 1, wherein the third chemical fluid is water.
 19. The method of claim 9, wherein the first chemical fluid comprises ions that affect the second chemical fluid concentration.
 20. The method of claim 9, wherein the second chemical fluid comprises ions that affect the first chemical fluid concentration. 